In the past two decades, the dye-sensitized solar cell (DSSC) has drawn much interest owing to its low production cost and thereby its capability to replace conventional solar cells.1 For practical application of DSSCs, their long-term stability, as well as high efficiency, has been highly demanded. Volatile solvent electrolytes being commonly used in DSSCs with a high efficiency, however, have the restriction on guaranteeing the stability due to the evaporation or leakage of solvent. While non-volatile electrolytes with high stability such as ionic liquids, oligomers, conducting polymers, and hole conductors have been reported as alternatives to volatile solvent, employing these materials to DSSCs has limitations in their efficiency compared with using volatile solvent electrolytes. One of the possible reasons of these limitations would be the structure of photoelectrodes, which is commonly inconvenient for highly viscous, non-volatile electrolytes to penetrate the nanopores in photoelectrodes. Accordingly, it is possible that the electrodes with the novel structure suitable to non-volatile electrolytes considerably improve the performance of the DSSCs. Recently, the novel structures of a photoelectrode have been reported in the use of nanowires,2 nanotubes,3 and hollow spheres.4 In particular, the electrodes containing a hollow structure have shown significant potential to possess an outstanding light-harvesting efficiency.4 Moreover, the hollow structure of the electrodes would have an additional advantage owing to its large porosity - good permeability of non-volatile electrolytes with high viscosity. In this study, we report a novel approach preparing the electrodes consisting of TiO2 hollow spheres (HS electrodes) through paste method. The HS electrode shows a high area density and desirable thickness without cracks.